US20110077445A1 - Generating natural gas from heavy hydrocarbons - Google Patents
Generating natural gas from heavy hydrocarbons Download PDFInfo
- Publication number
- US20110077445A1 US20110077445A1 US12/962,302 US96230210A US2011077445A1 US 20110077445 A1 US20110077445 A1 US 20110077445A1 US 96230210 A US96230210 A US 96230210A US 2011077445 A1 US2011077445 A1 US 2011077445A1
- Authority
- US
- United States
- Prior art keywords
- gas
- catalyst
- natural gas
- transition metal
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 64
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 64
- 239000003345 natural gas Substances 0.000 title claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 39
- 150000003624 transition metals Chemical class 0.000 claims abstract description 39
- 230000000638 stimulation Effects 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 7
- 239000011435 rock Substances 0.000 claims description 42
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 239000001307 helium Substances 0.000 claims description 17
- 229910052734 helium Inorganic materials 0.000 claims description 17
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052762 osmium Inorganic materials 0.000 claims description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052702 rhenium Inorganic materials 0.000 claims description 5
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052785 arsenic Inorganic materials 0.000 claims description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000005755 formation reaction Methods 0.000 description 17
- 239000010426 asphalt Substances 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000007327 hydrogenolysis reaction Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- -1 bitumen Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 235000015076 Shorea robusta Nutrition 0.000 description 3
- 244000166071 Shorea robusta Species 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000739 chaotic effect Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 235000004936 Bromus mango Nutrition 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001093152 Mangifera Species 0.000 description 1
- 235000014826 Mangifera indica Nutrition 0.000 description 1
- 235000009184 Spondias indica Nutrition 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/845—Compositions based on water or polar solvents containing inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
Definitions
- the invention relates in general to the production of natural gas from high molecular weight hydrocarbons and more particularly to generating natural gas from high molecular weight hydrocarbons.
- Heavy hydrocarbons such as bitumen, kerogen, GILSONITE (a registered trademark of American Gilsonite Company for a mineral known as asphaltum, uintaite or uintahite), and tars are high molecular weight hydrocarbons frequently encountered in subterranean formations. These hydrocarbons range from thick viscous liquids to solids at ambient temperatures and are generally quite expensive to recover in useful form.
- Bitumen occurs naturally in tar sands in locations such as Alberta, Canada and in the Orinoco oil belt north of the Orinoco river in Venezuela. Kerogens are the precursors to fossil fuels, and are also the material that forms oil shales. Kerogens, believed to be the precursor to bitumens, are frequently found in sedimentary rock formations.
- Heavy hydrocarbons in general have been used in a number of applications such as in asphalt and tar compositions for paving roads and roofing applications and as an ingredient in waterproofing formulations. Importantly, they are a potentially valuable feedstock for generating lighter hydrocarbons. This is typically accomplished by thermal cracking and hydrogenolysis processes, for example.
- An exemplary embodiment of a method of producing natural gas from heavy hydrocarbons in a reactor in accordance with the invention includes mixing heavy hydrocarbons and a catalyst comprising a transition metal forming a heavy hydrocarbon catalyst mixture; flowing, in the reactor, an anoxic stimulation gas having a concentration of less than 1 ppm O 2 , wherein the anoxic stimulation gas is not hydrogen; heating, in the reactor, the heavy hydrocarbon catalyst mixture in the presence of the anoxic stimulation gas; and generating a catalytic natural gas from the heavy hydrocarbons by a disproportionation reaction promoted by the catalyst.
- the catalyst is isolated from a source rock.
- the heavy hydrocarbons in the mixture are isolated from a source rock.
- the mixture may comprise a source rock having heavy hydrocarbons and the catalyst.
- mixing can comprise grinding a source rock comprising the heavy hydrocarbons and the catalyst.
- the catalyst may be supplied in the anoxic stimulation gas.
- the anoxic stimulation gas includes a gas selected from the group consisting of natural gas, carbon dioxide, helium, argon, and nitrogen. According to aspects of the invention, the anoxic stimulation gas is not comprised substantially of hydrogen.
- the anoxic stimulation gas can include the catalytic natural gas that is generated in the reactor.
- the transition metal is selected from the group consisting of molybdenum, nickel, cobalt, iron, copper, palladium, platinum, rhodium, ruthenium, tungsten, osmium, rhenium, and iridium; and the catalyst further comprises salts of a main group element selected from the group consisting of sulfur, phosphorus, arsenic, and antimony.
- an exemplary embodiment of a method for catalytic generation of natural gas comprises creating an anoxic condition in a reactor containing a mixture of heavy hydrocarbons and a catalyst comprising a transition metal; heating the mixture in the anoxic conditions of the reactor; and generating in the reactor a catalytic natural gas from the heavy hydrocarbons by a disproportionation reaction promoted by the catalyst.
- the mixture can include a source rock comprising the heavy hydrocarbons and the catalyst.
- the heavy hydrocarbons and/or the catalyst in the mixture may be isolated from a source rock.
- Creating the anoxic condition can include flowing an anoxic stimulation gas having a concentration of less than 1 ppm O 2 in the reactor.
- the anoxic stimulation gas is not substantially hydrogen (e.g., not pure hydrogen).
- the anoxic stimulation gas can include a gas selected from the group consisting of natural gas, carbon dioxide, helium, argon, and nitrogen.
- the natural gas can comprise the catalytic natural gas that is generated in the reactor.
- Another exemplary method for forming natural gas includes providing a mixture of heavy hydrocarbons and a catalyst having at least one transition metal; adding an anoxic stimulation gas to the mixture, and heating the mixture in the presence of the stimulation gas.
- FIG. 1 is a plot showing the generation of methane over time from Barnett Shale in flowing helium at 250° C. (degrees Celsius).
- FIG. 2 is a plot showing the generation of methane over time from Monterey source rock KG-4 in flowing helium at 250° C.
- Embodiments disclosed herein are directed to methods in which various transition metal-containing catalysts present as zero- or low-valent metal complexes, are co-injected with sand or other proppant into reservoirs rocks under sufficiently high pressures to fracture the rocks thus creating conduits of porous sand through which the transition metal complexes can pass into the regions of the formation containing heavy hydrocarbon materials.
- the catalysts may be delivered to hydrocarbon-containing sites within a formation using muds.
- a method of producing natural gas from a heavy hydrocarbon-containing subterranean formation includes placing a catalyst which has at least one transition metal into the formation, injecting an anoxic stimulation gas into the formation (in some embodiments simultaneous with catalyst introduction), and collecting the natural gas generated in the formation.
- Heavy Hydrocarbons as used herein include, but are not limited to all forms of carbonaceous deposits with sufficient hydrogen to convert to natural gas: (—CHx-) ⁇ gas+(—CHy-) where x>y. Examples include kerogens, solid hydrocarbons (GILSONITE, tars and the like), and bitumens. Such heavy hydrocarbons may be processed in situ in a formation. Alternatively, any of the hydrocarbons may also be reacted outside the context of a subterranean location, for example, in a batch reactor under carefully controlled conditions. Such conditions would include, for example, the substantial removal of oxygen which is prone to poisoning transition metal catalysts.
- Typical source rocks usually shales or limestones, contain about 1% organic matter, although a rich source rock might have as much as 20%.
- Source rocks convert their bitumen to natural gas at moderate temperatures (200° C.) in their natural state without hydrogen addition (see Experimental examples below). They do so chaotically, with random bursts of activity within periods of little or no activity, a phenomenon not uncommon in transition metal catalysis. Such behavior has been observed in a number of hydrogenation reactions including the hydrogenation of carbon monoxide, ethylene, and nitric oxide over Ni, Pt, Pd, Ir, Rh, and Ag (Eiswirth, M., 1993, Chaos in surface-catalyzed reactions; Ch. 6 in Chaos in Chemistry & Biochemistry, eds.
- the method of converting heavy hydrocarbons to natural gas may be accelerated in situ by injecting transition metals into reservoir rocks.
- the catalyst components may be obtained from an active source rock by isolation of the transition metals from active source rock.
- the source rock itself may be used without isolation of the individual active transition metals by generating a fine powder form of the source rock.
- high catalytic activity may be achieved by having catalyst particles with large surface area to volume ratios.
- it may be particularly beneficial to mill the source rock to very small particle size, for example, 10 nm-10,000 nm average diameter, though larger particles may be used as well.
- purified reagent grade transition metal components may be used and mixed in appropriate concentrations to reflect the naturally occurring compositions.
- active source rocks may contain sufficient low-valent transition metals (100 to 10,000 ppb) to promote the reaction at reservoir temperatures (100° C. to 200+° C.) on a production time scale (days to years).
- Source rock activities may be determined experimentally in flowing helium at various temperatures. An assay procedure has been described by Mango (U.S. Pat. No. 7,153,688).
- the transition metal may be a zero-valent transition metal, a low-valent transition metal, alloys, and mixtures thereof. Any transition metal that serves as a hydrogenation catalyst may be viable as a catalyst for the disproportionation reaction of heavy hydrocarbons.
- Various transition metals catalyze the hydrogenolysis of hydrocarbons to gas (Somorjai, G. A., 1994, Introduction to Surface Chemistry and Catalysis, John Wiley & Sons, New York, pg. 526); for example, C 2 H 6 +H 2 ⁇ 2 CH 4 . It has also been demonstrated that source rocks are catalytic in the hydrogenolysis of hydrocarbons (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas, Org. Geochem.
- low-valent transition metals are catalytic in the hydrogenolysis of crude oil (Mango, F. D., Hightower, J. W., and James, A. T. (1994) Role of transition-metal catalysis in the formation of natural gas, Nature, 368, 536-538.). Furthermore, there is substantial evidence that low-valent transition metals are active agents in sedimentary rocks (U.S. Pat. No. 7,153,688). Active source rock may include transition metals such as molybdenum, nickel, cobalt, iron, copper, palladium, platinum, rhodium, ruthenium, tungsten, rhenium, osmium, and iridium.
- the catalyst components may be immobilized and introduced into the subterranean formation on a proppant, in some embodiments.
- catalysts may be injected as gases, metal carbonyls, for example, which could dissolve in the carbonaceous sediments, decompose with time, thus delivering to the sediments low-valent active metals such as Ni, Co, Fe.
- the catalyst may be introduced at various stages in oil-based muds, for example. Fine metal particles could also be injected directly with sand in reservoir fracturing, thus dispersing fine particles of active catalyst throughout the network of porous sand conduits that carry hydrocarbons from the reservoir to the surface.
- Catalysts may be coated with paraffins (C 8 to C 18 ) to protect them from oxygen-poisoning while on the surface.
- Stimulation gas Since active metals in natural sedimentary rocks are poisoned irreversibly by oxygen (U.S. Pat. No. 7,153,688), it is beneficial that the stimulation be anoxic ( ⁇ 1 ppm O 2 ). Trace amounts of oxygen picked up in processing can be easily and inexpensively removed with commercial oxygen scrubbers.
- the stimulation gas may include natural gas, gas depleted of methane, carbon dioxide, helium, argon, and nitrogen.
- hydrogen gas may interfere with separation and therefore is not an ideal stimulation gas.
- the stimulation gas may be the same gas used in fracturing the formation or may be different from that used in fracturing the formation.
- the stimulation gas may also be used not only for the fracturing, but also as a means of depositing the catalyst within the formation.
- the stimulation of catalytic gas generation from bitumen in reservoir rocks may be achieved through a single wellbore in a permeable reservoirs by injecting and withdrawing gas sequentially to create sufficient turbulence to stimulate chaotic gas generation or it may be achieved through multiple injection wells positioned to maximize continuous gas flow through the permeable reservoir to production wells that collect the injected gas plus catalytic gas. Production units would collect produced gas, injecting a fraction to maintain a continuous process and sending the remainder to market.
- Fracturing may be accomplished with injected sand or other appropriate proppant to create interlacing conduits of porous sand to carry injected gas through the reservoir to conduits of porous sands that carry the injected gas plus catalytic gas from the reservoir to production units.
- the flowing gas injected into the reservoir stimulates catalytic activity within the shale.
- Injected gas may be natural gas produced from the deposit or natural gas produced from another deposit elsewhere.
- the process could be carried out by sequential injections where the reservoir is pressured, then allowed to stand and exhaust its induced pressure over time. This process could be repeated multiple times until the reservoir was exhausted of heavy hydrocarbons.
- the process could also be carried out in a continuous mode where gas is injected continuously into one well and withdrawn continuously from another.
- the two wells (or multiple wells) would be interconnected through a production unit that withdraws produced gas from the system sending excess gas to market and re-injecting the remainder to sustain continuous production.
- Heavy hydrocarbon to natural gas In addition to methods for in situ cracking of heavy hydrocarbons in a subterranean location, one may also produce natural gas from isolated heavy hydrocarbons in batch reactors, for example. To carry out such production the method entails mixing isolated heavy hydrocarbons (for example mined bitumen) with an active catalyst as described above. An anoxic stimulation gas may be introduced and the mixture heated under anoxic conditions.
- the catalyst may be an active source rock ground into fine powder as described above.
- the active transition metal components may be isolated from the source rock or stock mixtures prepared from commercially available sources in proportions identified in high activity source rock.
- the stimulation gas may be natural gas, natural gas depleted of methane, carbon dioxide, helium, argon, and nitrogen. In the context of batch reaction, such a stimulation gas may be provided as a flow while heating the bitumen catalyst mixture. Catalytic activity may be facilitated by heating in a range from about 25° C. to about 350° C. and from about 25° C. to about 250° C. in other embodiments. In particular embodiments, heating may be carried out in a range from about 100° C. to about 200° C. In all embodiments, it is beneficial that the stimulation gas be anoxic ( ⁇ 1 pp O 2 ).
- Methods disclosed herein may be used in the production of natural gas (catalytic gas).
- the aforementioned method for the disproportionation of bitumen and high molecular weight hydrocarbons may be used in such production. This may be carried out in batch reactors, or generated directly from tar sand sources where it may be collected in the field and distributed commercially.
- Barnett Shale 250° C., Helium.
- Helium flow (12 mL/min) was continued at 250° C. for over one hour while the effluent (i.e., stimulation) gas was monitored for methane by standard gas chromatographic (gc) analysis ( FIG. 1 ).
- the first methane peak (presumably adsorbed and catalytic methane from the 10 min purge at 350° C.) emerged at 12.5 min (5.8 ⁇ 10 ⁇ 5 g CH 4 ) followed by a flat baseline over the next 20 min showing that the sample was no longer releasing methane.
- Three sharp peaks of increasing intensity then appeared at 45 min. (9.9 ⁇ 10 ⁇ 6 g CH 4 ), 68 min. (1.6 ⁇ 10 ⁇ 5 g CH 4 ), and 94 min. (5.6 ⁇ 10 ⁇ 5 g CH 4 ).
- the final three peaks constitute 2.2 ⁇ 10 ⁇ 2 mg CH 4 /(g rock hr) which is greater than that for this rock under our usual conditions (in hydrogen) (5.7 ⁇ 10 ⁇ 3 mg CH 4 /(g rock hr).
- the initial peak of adsorbed gas (3 min., 2.7 ⁇ 10 ⁇ 6 g CH 4 )
- three very large peaks emerged after 5 hours of He flow the first corresponding to 7.3 ⁇ 10 ⁇ 4 g CH 4
- Barnett Shale 200° C., Helium. Pure helium (passed through an oxygen scrubber) was passed over a sample of Barnett Shale (2.88 g) (ground to a powder (60 mesh) in argon) at 200° C. for 140 minutes producing a burst of methane (4 ⁇ 10 ⁇ 2 mg) corresponding to a rate of 8.3 ⁇ 10 ⁇ 3 mg CH 4 /(g rock hr), a rate substantially greater than that obtained from the same experiment in hydrogen (3.6 ⁇ 10 ⁇ 5 mg CH 4 /(g rock hr)) at this temperature and only slightly lower than that at 250° C.
- a Monterey shale (Miocene, Calif.) sample generates methane at a rate of ⁇ 6 ⁇ 10 ⁇ 6 g C 1 /(g rock hr) in hydrogen gas containing 3% propane under closed conditions (30 minutes) at 250° C. and generates very little methane at 200° C. under the same conditions (30 minutes). Under flowing helium at 200° C., the same rock converts its bitumen to gas at a rate of 1.3 ⁇ 10 ⁇ 4 g C 1 /(g rock hr).
- mass-transfer stimulation gas may achieve two positive effects: 1) it transports hydrocarbons from heavy hydrocarbon deposits to active catalytic sites, and 2) it removes activity-suppressing agents (products and adsorbents) from the active sites catalyst surfaces.
- the methods describe herein provide a means for recovery useful catalytic gas from heavy hydrocarbons in situ from subterranean formations.
- the conversion of heavy hydrocarbon extends the useful lifetime of reservoir enhancing the oil recovery process.
- the same process may be duplicated under controlled conditions in batch reactors for commercial production of natural gas.
- the availability of certain heavy hydrocarbons, such as bitumen, from renewable resources may provide an environmentally sound means for natural gas production.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
- This application is a continuation of Ser. No. 12/159,962, filed on Jul. 2, 2008, now U.S. Pat. No. 7,845,414, issued Dec. 7, 2010, which is a national stage entry of PCT/US2007/060215, filed on Jan. 8, 2007, which is a non-provisional of Ser. No. 60/757,168, filed on Jan. 6, 2006.
- The invention relates in general to the production of natural gas from high molecular weight hydrocarbons and more particularly to generating natural gas from high molecular weight hydrocarbons.
- This section provides background information to facilitate a better understanding of the various aspects of the invention. It should be understood that the statements in this section of this document are to be read in this light, and not as admissions of prior art.
- Heavy hydrocarbons such as bitumen, kerogen, GILSONITE (a registered trademark of American Gilsonite Company for a mineral known as asphaltum, uintaite or uintahite), and tars are high molecular weight hydrocarbons frequently encountered in subterranean formations. These hydrocarbons range from thick viscous liquids to solids at ambient temperatures and are generally quite expensive to recover in useful form. Bitumen occurs naturally in tar sands in locations such as Alberta, Canada and in the Orinoco oil belt north of the Orinoco river in Venezuela. Kerogens are the precursors to fossil fuels, and are also the material that forms oil shales. Kerogens, believed to be the precursor to bitumens, are frequently found in sedimentary rock formations.
- Heavy hydrocarbons in general, have been used in a number of applications such as in asphalt and tar compositions for paving roads and roofing applications and as an ingredient in waterproofing formulations. Importantly, they are a potentially valuable feedstock for generating lighter hydrocarbons. This is typically accomplished by thermal cracking and hydrogenolysis processes, for example.
- Recovering heavy hydrocarbons whole or as lighter hydrocarbons and/or natural gas by thermal cracking in subterranean formations continues to be a challenge. The excessive temperatures necessary for thermal (or steam) cracking (about 850° C.) requires expensive, complex technology due to the special construction material to sustain high cracking temperatures and high energy input. Hydrogenolysis has limited utility when the recovery of lighter hydrocarbons is desirable. This is due to the difficulty of separating hydrogen from light olefins such as ethylene, propylene, and natural gas. Therefore, there is a continuing need for the development of methods for producing light hydrocarbons and natural gas from high molecular weight hydrocarbon feedstock.
- An exemplary embodiment of a method of producing natural gas from heavy hydrocarbons in a reactor in accordance with the invention includes mixing heavy hydrocarbons and a catalyst comprising a transition metal forming a heavy hydrocarbon catalyst mixture; flowing, in the reactor, an anoxic stimulation gas having a concentration of less than 1 ppm O2, wherein the anoxic stimulation gas is not hydrogen; heating, in the reactor, the heavy hydrocarbon catalyst mixture in the presence of the anoxic stimulation gas; and generating a catalytic natural gas from the heavy hydrocarbons by a disproportionation reaction promoted by the catalyst.
- In at least one embodiment the catalyst is isolated from a source rock. In some embodiments the heavy hydrocarbons in the mixture are isolated from a source rock. In some embodiment the mixture may comprise a source rock having heavy hydrocarbons and the catalyst. For example, mixing can comprise grinding a source rock comprising the heavy hydrocarbons and the catalyst. In some embodiments, the catalyst may be supplied in the anoxic stimulation gas.
- In some embodiments the anoxic stimulation gas includes a gas selected from the group consisting of natural gas, carbon dioxide, helium, argon, and nitrogen. According to aspects of the invention, the anoxic stimulation gas is not comprised substantially of hydrogen. The anoxic stimulation gas can include the catalytic natural gas that is generated in the reactor.
- In at least one embodiment the transition metal is selected from the group consisting of molybdenum, nickel, cobalt, iron, copper, palladium, platinum, rhodium, ruthenium, tungsten, osmium, rhenium, and iridium; and the catalyst further comprises salts of a main group element selected from the group consisting of sulfur, phosphorus, arsenic, and antimony.
- According to one or more aspects of the invention, an exemplary embodiment of a method for catalytic generation of natural gas comprises creating an anoxic condition in a reactor containing a mixture of heavy hydrocarbons and a catalyst comprising a transition metal; heating the mixture in the anoxic conditions of the reactor; and generating in the reactor a catalytic natural gas from the heavy hydrocarbons by a disproportionation reaction promoted by the catalyst.
- The mixture can include a source rock comprising the heavy hydrocarbons and the catalyst. The heavy hydrocarbons and/or the catalyst in the mixture may be isolated from a source rock.
- Creating the anoxic condition can include flowing an anoxic stimulation gas having a concentration of less than 1 ppm O2 in the reactor. According to one or more aspects of the invention, the anoxic stimulation gas is not substantially hydrogen (e.g., not pure hydrogen). The anoxic stimulation gas can include a gas selected from the group consisting of natural gas, carbon dioxide, helium, argon, and nitrogen. The natural gas can comprise the catalytic natural gas that is generated in the reactor.
- Another exemplary method for forming natural gas includes providing a mixture of heavy hydrocarbons and a catalyst having at least one transition metal; adding an anoxic stimulation gas to the mixture, and heating the mixture in the presence of the stimulation gas.
- The foregoing has outlined some of the features and technical advantages of the invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention.
- The foregoing and other features and aspects of the invention will be best understood with reference to the following detailed description of specific embodiments of the invention, when read in conjunction with the accompanying drawings, wherein:
-
FIG. 1 is a plot showing the generation of methane over time from Barnett Shale in flowing helium at 250° C. (degrees Celsius). -
FIG. 2 is a plot showing the generation of methane over time from Monterey source rock KG-4 in flowing helium at 250° C. - Embodiments disclosed herein are directed to methods in which various transition metal-containing catalysts present as zero- or low-valent metal complexes, are co-injected with sand or other proppant into reservoirs rocks under sufficiently high pressures to fracture the rocks thus creating conduits of porous sand through which the transition metal complexes can pass into the regions of the formation containing heavy hydrocarbon materials. Alternatively, the catalysts may be delivered to hydrocarbon-containing sites within a formation using muds.
- The method further includes closing the well (after introduction of stimulation gases) for sufficient time to allow metal catalyzed decomposition of bitumen (digestion) and gas generation. Thus, a method of producing natural gas from a heavy hydrocarbon-containing subterranean formation includes placing a catalyst which has at least one transition metal into the formation, injecting an anoxic stimulation gas into the formation (in some embodiments simultaneous with catalyst introduction), and collecting the natural gas generated in the formation.
- Heavy Hydrocarbons: Heavy hydrocarbons as used herein include, but are not limited to all forms of carbonaceous deposits with sufficient hydrogen to convert to natural gas: (—CHx-)→gas+(—CHy-) where x>y. Examples include kerogens, solid hydrocarbons (GILSONITE, tars and the like), and bitumens. Such heavy hydrocarbons may be processed in situ in a formation. Alternatively, any of the hydrocarbons may also be reacted outside the context of a subterranean location, for example, in a batch reactor under carefully controlled conditions. Such conditions would include, for example, the substantial removal of oxygen which is prone to poisoning transition metal catalysts.
- Catalyst: Typical source rocks, usually shales or limestones, contain about 1% organic matter, although a rich source rock might have as much as 20%. Source rocks convert their bitumen to natural gas at moderate temperatures (200° C.) in their natural state without hydrogen addition (see Experimental examples below). They do so chaotically, with random bursts of activity within periods of little or no activity, a phenomenon not uncommon in transition metal catalysis. Such behavior has been observed in a number of hydrogenation reactions including the hydrogenation of carbon monoxide, ethylene, and nitric oxide over Ni, Pt, Pd, Ir, Rh, and Ag (Eiswirth, M., 1993, Chaos in surface-catalyzed reactions; Ch. 6 in Chaos in Chemistry & Biochemistry, eds. R. J. Field & L. Gyorgyi, World Scientific Publishing Co., River Edge, N.J., USA, 141-174.) and in the hydrogenolysis of ethane over Ni and Pd (Kristyan, S., and Szamosi, J., 1992, Reaction kinetic surfaces and isosurfaces of the catalytic hydrogenolysis of ethane and its self-poisoning over Ni and Pd catalysts; Computers in Physics 6, 494-497.). Indeed, such chaotic behavior is an identifying characteristic of transition metal catalysis.
- Therefore, in some embodiments, the method of converting heavy hydrocarbons to natural gas (oil-to-gas) may be accelerated in situ by injecting transition metals into reservoir rocks. The catalyst components may be obtained from an active source rock by isolation of the transition metals from active source rock. Alternatively, the source rock itself may be used without isolation of the individual active transition metals by generating a fine powder form of the source rock. One skilled in the art will recognize that under heterogeneous conditions high catalytic activity may be achieved by having catalyst particles with large surface area to volume ratios. Thus, it may be particularly beneficial to mill the source rock to very small particle size, for example, 10 nm-10,000 nm average diameter, though larger particles may be used as well.
- In yet other embodiments, purified reagent grade transition metal components may be used and mixed in appropriate concentrations to reflect the naturally occurring compositions. For example, active source rocks may contain sufficient low-valent transition metals (100 to 10,000 ppb) to promote the reaction at reservoir temperatures (100° C. to 200+° C.) on a production time scale (days to years). Source rock activities may be determined experimentally in flowing helium at various temperatures. An assay procedure has been described by Mango (U.S. Pat. No. 7,153,688).
- The transition metal may be a zero-valent transition metal, a low-valent transition metal, alloys, and mixtures thereof. Any transition metal that serves as a hydrogenation catalyst may be viable as a catalyst for the disproportionation reaction of heavy hydrocarbons. Various transition metals catalyze the hydrogenolysis of hydrocarbons to gas (Somorjai, G. A., 1994, Introduction to Surface Chemistry and Catalysis, John Wiley & Sons, New York, pg. 526); for example, C2H6+H2→2 CH4. It has also been demonstrated that source rocks are catalytic in the hydrogenolysis of hydrocarbons (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas, Org. Geochem. 24, 977-984.) and that low-valent transition metals are catalytic in the hydrogenolysis of crude oil (Mango, F. D., Hightower, J. W., and James, A. T. (1994) Role of transition-metal catalysis in the formation of natural gas, Nature, 368, 536-538.). Furthermore, there is substantial evidence that low-valent transition metals are active agents in sedimentary rocks (U.S. Pat. No. 7,153,688). Active source rock may include transition metals such as molybdenum, nickel, cobalt, iron, copper, palladium, platinum, rhodium, ruthenium, tungsten, rhenium, osmium, and iridium.
- The catalyst components may be immobilized and introduced into the subterranean formation on a proppant, in some embodiments. Alternatively, catalysts may be injected as gases, metal carbonyls, for example, which could dissolve in the carbonaceous sediments, decompose with time, thus delivering to the sediments low-valent active metals such as Ni, Co, Fe. Alternatively, the catalyst may be introduced at various stages in oil-based muds, for example. Fine metal particles could also be injected directly with sand in reservoir fracturing, thus dispersing fine particles of active catalyst throughout the network of porous sand conduits that carry hydrocarbons from the reservoir to the surface. Catalysts may be coated with paraffins (C8 to C18) to protect them from oxygen-poisoning while on the surface.
- Stimulation gas: Since active metals in natural sedimentary rocks are poisoned irreversibly by oxygen (U.S. Pat. No. 7,153,688), it is beneficial that the stimulation be anoxic (<1 ppm O2). Trace amounts of oxygen picked up in processing can be easily and inexpensively removed with commercial oxygen scrubbers. The stimulation gas may include natural gas, gas depleted of methane, carbon dioxide, helium, argon, and nitrogen. For natural gas (catalytic gas) production, hydrogen gas may interfere with separation and therefore is not an ideal stimulation gas. The stimulation gas may be the same gas used in fracturing the formation or may be different from that used in fracturing the formation. Again, the stimulation gas may also be used not only for the fracturing, but also as a means of depositing the catalyst within the formation. In some embodiments, the stimulation of catalytic gas generation from bitumen in reservoir rocks may be achieved through a single wellbore in a permeable reservoirs by injecting and withdrawing gas sequentially to create sufficient turbulence to stimulate chaotic gas generation or it may be achieved through multiple injection wells positioned to maximize continuous gas flow through the permeable reservoir to production wells that collect the injected gas plus catalytic gas. Production units would collect produced gas, injecting a fraction to maintain a continuous process and sending the remainder to market.
- In reservoirs with insufficient permeability to sustain gas flow such as tight shales like the Mississippian Barnett Shale in the Fort Worth Basin (Tex.), fracturing the reservoir may be beneficial. Fracturing may be accomplished with injected sand or other appropriate proppant to create interlacing conduits of porous sand to carry injected gas through the reservoir to conduits of porous sands that carry the injected gas plus catalytic gas from the reservoir to production units. The flowing gas injected into the reservoir stimulates catalytic activity within the shale.
- Injected gas may be natural gas produced from the deposit or natural gas produced from another deposit elsewhere. The process could be carried out by sequential injections where the reservoir is pressured, then allowed to stand and exhaust its induced pressure over time. This process could be repeated multiple times until the reservoir was exhausted of heavy hydrocarbons. The process could also be carried out in a continuous mode where gas is injected continuously into one well and withdrawn continuously from another. The two wells (or multiple wells) would be interconnected through a production unit that withdraws produced gas from the system sending excess gas to market and re-injecting the remainder to sustain continuous production.
- Heavy hydrocarbon to natural gas: In addition to methods for in situ cracking of heavy hydrocarbons in a subterranean location, one may also produce natural gas from isolated heavy hydrocarbons in batch reactors, for example. To carry out such production the method entails mixing isolated heavy hydrocarbons (for example mined bitumen) with an active catalyst as described above. An anoxic stimulation gas may be introduced and the mixture heated under anoxic conditions.
- Again the catalyst may be an active source rock ground into fine powder as described above. Alternatively, the active transition metal components may be isolated from the source rock or stock mixtures prepared from commercially available sources in proportions identified in high activity source rock.
- The stimulation gas may be natural gas, natural gas depleted of methane, carbon dioxide, helium, argon, and nitrogen. In the context of batch reaction, such a stimulation gas may be provided as a flow while heating the bitumen catalyst mixture. Catalytic activity may be facilitated by heating in a range from about 25° C. to about 350° C. and from about 25° C. to about 250° C. in other embodiments. In particular embodiments, heating may be carried out in a range from about 100° C. to about 200° C. In all embodiments, it is beneficial that the stimulation gas be anoxic (<1 pp O2).
- Methods disclosed herein may be used in the production of natural gas (catalytic gas). The aforementioned method for the disproportionation of bitumen and high molecular weight hydrocarbons may be used in such production. This may be carried out in batch reactors, or generated directly from tar sand sources where it may be collected in the field and distributed commercially.
- The following example is included to demonstrate particular embodiments of the invention. It should be appreciated by those of skill in the art that the methods disclosed in the example that follows merely represent exemplary embodiments of the invention. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments described and still obtain a like or similar result without departing from the spirit and scope of the invention.
- Barnett Shale, 250° C., Helium. A sample of Barnett shale (Mississippian, Ft. Worth Basin Tex.) (3.4 g), ground to a powder in anoxic argon, was placed in a reactor and purged of any adsorbed oxygen by flowing anoxic helium (through a commercial oxygen scrubber) through the reactor at 350° C. for 20 minutes. Helium flow (12 mL/min) was continued at 250° C. for over one hour while the effluent (i.e., stimulation) gas was monitored for methane by standard gas chromatographic (gc) analysis (
FIG. 1 ). The first methane peak (presumably adsorbed and catalytic methane from the 10 min purge at 350° C.) emerged at 12.5 min (5.8×10−5 g CH4) followed by a flat baseline over the next 20 min showing that the sample was no longer releasing methane. Three sharp peaks of increasing intensity then appeared at 45 min. (9.9×10−6 g CH4), 68 min. (1.6×10−5 g CH4), and 94 min. (5.6×10−5 g CH4). The final three peaks constitute 2.2×10−2 mg CH4/(g rock hr) which is greater than that for this rock under our usual conditions (in hydrogen) (5.7×10−3 mg CH4/(g rock hr). - Monterey Source Rock, 250° C., Helium. A sample of Monterey shale (Miocene, Calif.) (KG-4) (1.64 g) was analyzed under identical conditions under pure helium flow for about 7 hours (
FIG. 2 ). After the initial peak of adsorbed gas (3 min., 2.7×10−6 g CH4), three very large peaks emerged after 5 hours of He flow, the first corresponding to 7.3×10−4 g CH4, the second (180 min. later) to 2.2×10−4 g CH4, and the third (285 min. after the first) to 1.1×10−4 g CH4, with an overall rate of 0.2 mg CH4/(g rock hr), not materially different from that under hydrogen. - Barnett Shale, 200° C., Helium. Pure helium (passed through an oxygen scrubber) was passed over a sample of Barnett Shale (2.88 g) (ground to a powder (60 mesh) in argon) at 200° C. for 140 minutes producing a burst of methane (4×10−2 mg) corresponding to a rate of 8.3×10−3 mg CH4/(g rock hr), a rate substantially greater than that obtained from the same experiment in hydrogen (3.6×10−5 mg CH4/(g rock hr)) at this temperature and only slightly lower than that at 250° C.
- It was observed that activity increases only slightly with temperature in helium suggesting rate suppression counteracting the usual Arrhenius exponential rate increase with temperature. The higher-than-expected activities observed in helium at 200° C. suggests higher than anticipated activities at subsurface temperatures and the expectation of promoting the conversion of heavy hydrocarbon to natural gas at moderate reservoir temperatures by injecting low-valent active transition metals into these reservoirs.
- A Monterey shale (Miocene, Calif.) sample generates methane at a rate of ˜6×10−6 g C1/(g rock hr) in hydrogen gas containing 3% propane under closed conditions (30 minutes) at 250° C. and generates very little methane at 200° C. under the same conditions (30 minutes). Under flowing helium at 200° C., the same rock converts its bitumen to gas at a rate of 1.3×10−4 g C1/(g rock hr). These results suggest that the mass-transfer stimulation gas may achieve two positive effects: 1) it transports hydrocarbons from heavy hydrocarbon deposits to active catalytic sites, and 2) it removes activity-suppressing agents (products and adsorbents) from the active sites catalyst surfaces.
- Advantageously, the methods describe herein provide a means for recovery useful catalytic gas from heavy hydrocarbons in situ from subterranean formations. When used in situ at the site of a formation, the conversion of heavy hydrocarbon extends the useful lifetime of reservoir enhancing the oil recovery process. The same process may be duplicated under controlled conditions in batch reactors for commercial production of natural gas. Furthermore, the availability of certain heavy hydrocarbons, such as bitumen, from renewable resources may provide an environmentally sound means for natural gas production.
- All patents and publications referenced herein are hereby incorporated by reference to the extent not inconsistent herewith. It will be understood that certain of the above-described structures, functions, and operations of the above-described embodiments are not necessary to practice the invention and are included in the description simply for completeness of an exemplary embodiment or embodiments. In addition, it will be understood that specific structures, functions, and operations set forth in the above-described referenced patents and publications can be practiced in conjunction with the invention, but they are not essential to its practice. It is therefore to be understood that the invention may be practiced otherwise than as specifically described without actually departing from the spirit and scope of the invention as defined by the appended claim.
- From the foregoing detailed description of specific embodiments of the invention, it should be apparent that a novel method for converting bitumen to natural gas has been disclosed. Although specific embodiments of the invention have been disclosed herein in some detail, this has been done solely for the purposes of describing various features and aspects of the invention, and is not intended to be limiting with respect to the scope of the invention. It is contemplated that various substitutions, alterations, and/or modifications, including but not limited to those implementation variations which may have been suggested herein, may be made to the disclosed embodiments without departing from the spirit and scope of the invention as defined by the appended claims which follow.
Claims (20)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/962,302 US8273937B2 (en) | 2006-01-06 | 2010-12-07 | Generating natural gas from heavy hydrocarbons |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US75716806P | 2006-01-06 | 2006-01-06 | |
PCT/US2007/060215 WO2007082179A2 (en) | 2006-01-06 | 2007-01-08 | In situ conversion of heavy hydrocarbons to catalytic gas |
US15996208A | 2008-07-02 | 2008-07-02 | |
US12/962,302 US8273937B2 (en) | 2006-01-06 | 2010-12-07 | Generating natural gas from heavy hydrocarbons |
Related Parent Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/159,962 Continuation US7845414B2 (en) | 2006-01-06 | 2007-01-08 | In situ conversion of heavy hydrocarbons to catalytic gas |
PCT/US2007/060215 Continuation WO2007082179A2 (en) | 2006-01-06 | 2007-01-08 | In situ conversion of heavy hydrocarbons to catalytic gas |
US15996208A Continuation | 2006-01-06 | 2008-07-02 |
Publications (2)
Publication Number | Publication Date |
---|---|
US20110077445A1 true US20110077445A1 (en) | 2011-03-31 |
US8273937B2 US8273937B2 (en) | 2012-09-25 |
Family
ID=38257094
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/159,962 Expired - Fee Related US7845414B2 (en) | 2006-01-06 | 2007-01-08 | In situ conversion of heavy hydrocarbons to catalytic gas |
US12/962,302 Active US8273937B2 (en) | 2006-01-06 | 2010-12-07 | Generating natural gas from heavy hydrocarbons |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/159,962 Expired - Fee Related US7845414B2 (en) | 2006-01-06 | 2007-01-08 | In situ conversion of heavy hydrocarbons to catalytic gas |
Country Status (7)
Country | Link |
---|---|
US (2) | US7845414B2 (en) |
CN (1) | CN101395742A (en) |
AU (1) | AU2007204728A1 (en) |
BR (1) | BRPI0706846A2 (en) |
CA (1) | CA2636190A1 (en) |
RU (1) | RU2008130831A (en) |
WO (1) | WO2007082179A2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8273937B2 (en) | 2006-01-06 | 2012-09-25 | Petroleum Habitats, Llc | Generating natural gas from heavy hydrocarbons |
US8727006B2 (en) | 2010-05-04 | 2014-05-20 | Petroleum Habitats, Llc | Detecting and remedying hydrogen starvation of catalytic hydrocarbon generation reactions in earthen formations |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9033033B2 (en) | 2010-12-21 | 2015-05-19 | Chevron U.S.A. Inc. | Electrokinetic enhanced hydrocarbon recovery from oil shale |
US9133398B2 (en) | 2010-12-22 | 2015-09-15 | Chevron U.S.A. Inc. | In-situ kerogen conversion and recycling |
US8701788B2 (en) | 2011-12-22 | 2014-04-22 | Chevron U.S.A. Inc. | Preconditioning a subsurface shale formation by removing extractible organics |
US8851177B2 (en) | 2011-12-22 | 2014-10-07 | Chevron U.S.A. Inc. | In-situ kerogen conversion and oxidant regeneration |
US9181467B2 (en) | 2011-12-22 | 2015-11-10 | Uchicago Argonne, Llc | Preparation and use of nano-catalysts for in-situ reaction with kerogen |
US8992771B2 (en) | 2012-05-25 | 2015-03-31 | Chevron U.S.A. Inc. | Isolating lubricating oils from subsurface shale formations |
Citations (53)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2387513A (en) * | 1941-08-08 | 1945-10-23 | Standard Oil Dev Co | Well logging |
US2551449A (en) * | 1949-06-15 | 1951-05-01 | Nuclear Dev Associates Inc | Method for locating deposits |
US2705417A (en) * | 1951-12-21 | 1955-04-05 | Petroleum Engineering Associat | Mineralogical analysis |
US2768793A (en) * | 1954-03-22 | 1956-10-30 | Exxon Research Engineering Co | Disintegrator for rock and the like |
US2854396A (en) * | 1954-11-24 | 1958-09-30 | Jersey Prod Res Co | Petroleum prospecting |
US3033287A (en) * | 1959-08-04 | 1962-05-08 | Pure Oil Co | Geochemical process |
US3180902A (en) * | 1961-08-10 | 1965-04-27 | Engelhard Ind Inc | Process for the hydrogenolysis of light hydrocarbons |
US3322195A (en) * | 1964-01-20 | 1967-05-30 | Exxon Research Engineering Co | Process and apparatus for recovery of additional fuels from oil and gas wells |
US3343917A (en) * | 1963-11-22 | 1967-09-26 | Pan American Petroleum Corp | Obtaining paleoenvironmental information |
US3428431A (en) * | 1965-05-12 | 1969-02-18 | Sinclair Research Inc | Geochemical petroleum exploration method |
US3719453A (en) * | 1970-11-25 | 1973-03-06 | Phillips Petroleum Co | Detection of reducing conditions in a formation as in oil prospecting |
US3752984A (en) * | 1971-12-02 | 1973-08-14 | Texaco Inc | Methods and system for detecting subsurface minerals |
US3934455A (en) * | 1974-02-13 | 1976-01-27 | The Dow Chemical Company | Apparatus for testing a sand sample |
US4081675A (en) * | 1976-11-08 | 1978-03-28 | Phillips Petroleum Company | Geophysical and geochemical exploration |
US4108552A (en) * | 1976-06-29 | 1978-08-22 | Union Carbide Corporation | Method and system for detecting ultra-trace quantities of metal carbonyls |
US4205956A (en) * | 1979-05-21 | 1980-06-03 | The International Nickel Company, Inc. | Nickel carbonyl analyzer |
US4334882A (en) * | 1981-04-01 | 1982-06-15 | Mobil Oil Corporation | Determination of pyrite and siderite content of formation deposits |
US4345912A (en) * | 1980-09-12 | 1982-08-24 | Phillips Petroleum Company | Uranium prospecting based on selenium and molybdenum |
US4352673A (en) * | 1979-12-28 | 1982-10-05 | Institut Francais Du Petrole | Method and device for determining the organic carbon content of a sample |
US4385983A (en) * | 1981-08-10 | 1983-05-31 | Chevron Research Company | Process for retorting oil shale mixtures with added carbonaceous material |
US4426452A (en) * | 1982-05-27 | 1984-01-17 | Syngas Company | Volatile metal carbonyl analysis |
US4438816A (en) * | 1982-05-13 | 1984-03-27 | Uop Inc. | Process for recovery of hydrocarbons from oil shale |
US4507195A (en) * | 1983-05-16 | 1985-03-26 | Chevron Research Company | Coking contaminated oil shale or tar sand oil on retorted solid fines |
US4587847A (en) * | 1981-10-07 | 1986-05-13 | Boliden Aktiebolag | Method for indicating concealed deposits |
US4610776A (en) * | 1984-06-29 | 1986-09-09 | Uop Inc. | Coal liquefaction process |
US4681854A (en) * | 1982-05-28 | 1987-07-21 | Phillips Petroleum Company | Geochemical oil prospecting method using in situ simulation of diagenetic processes |
US4701270A (en) * | 1985-02-28 | 1987-10-20 | Canadian Fracmaster Limited | Novel compositions suitable for treating deep wells |
US4792526A (en) * | 1982-12-21 | 1988-12-20 | Union Oil Company Of California | Method for collecting and analyzing hydrocarbons |
US4798805A (en) * | 1985-04-05 | 1989-01-17 | Geoservices, Societe Anonyme | Apparatus and process for pyrolysis and analysis of samples containing organic matter |
US5082787A (en) * | 1989-12-22 | 1992-01-21 | Texaco Inc. | Method of performing hydrous pyrolysis for studying the kinetic parameters of hydrocarbons generated from source material |
US5097123A (en) * | 1990-02-07 | 1992-03-17 | Schlumberger Technology Corporation | Broad energy spectra neutron source for logging and method |
US5174966A (en) * | 1989-08-14 | 1992-12-29 | Institut Francis Du Petrole | Laboratory device and method for treating rock samples |
US5178837A (en) * | 1985-07-25 | 1993-01-12 | The British Petroleum Company P.L.C. | Rock analyzer |
US5389550A (en) * | 1992-03-13 | 1995-02-14 | Japan National Oil Corporation | Organic substance analyzing method and apparatus using portable construction |
US5769165A (en) * | 1996-01-31 | 1998-06-23 | Vastar Resources Inc. | Method for increasing methane recovery from a subterranean coal formation by injection of tail gas from a hydrocarbon synthesis process |
US6225359B1 (en) * | 1999-12-21 | 2001-05-01 | Chevron U.S.A. Inc. | Process for conversion of natural gas and associated light hydrocarbons to salable products |
US6229060B1 (en) * | 1996-07-12 | 2001-05-08 | Centre National De La Recherche Scientifique (C.N.R.S.) | Method of metathesis of alkanes and catalyst |
US20020002318A1 (en) * | 1999-06-11 | 2002-01-03 | O'rear Dennis J. | Process for conversion of well gas by disproporationation to saleable products |
US20020058581A1 (en) * | 2000-09-28 | 2002-05-16 | Fairmount Minerals, Ltd | Proppant composition for gas and oil well l fracturing |
US6666067B2 (en) * | 2001-06-07 | 2003-12-23 | Kathy Karol Stolper | Visual gas show identification method |
US20040016676A1 (en) * | 2002-07-24 | 2004-01-29 | Newton Jeffrey P. | Production of lower molecular weight dydrocarbons |
US6739394B2 (en) * | 2000-04-24 | 2004-05-25 | Shell Oil Company | Production of synthesis gas from a hydrocarbon containing formation |
US20040166582A1 (en) * | 2001-07-26 | 2004-08-26 | Alain Prinzhofer | Method for quantitative monitoring of a gas injected in a reservoir in particular in a natural environment |
US20050082058A1 (en) * | 2003-09-23 | 2005-04-21 | Bustin Robert M. | Method for enhancing methane production from coal seams |
US20050250209A1 (en) * | 2004-04-21 | 2005-11-10 | Petroleum Habitats, Llc | Determining metal content of source rock during well logging |
US20060065400A1 (en) * | 2004-09-30 | 2006-03-30 | Smith David R | Method and apparatus for stimulating a subterranean formation using liquefied natural gas |
US20060121615A1 (en) * | 2004-12-07 | 2006-06-08 | Petroleum Habitats, L.L.C. | Rock assay for predicting oil or gas in target reservoirs |
US20060117841A1 (en) * | 2004-12-07 | 2006-06-08 | Petroleum Habitats, L.L.C. | Novel well logging method for the determination of catalytic activity |
US20060191686A1 (en) * | 2005-02-25 | 2006-08-31 | Halliburton Energy Services, Inc. | Methods and compositions for the in-situ thermal stimulation of hydrocarbons using peroxide-generating compounds |
US20080115935A1 (en) * | 2006-01-06 | 2008-05-22 | Mango Frank D | In situ conversion of heavy hydrocarbons to catalytic gas |
US7435597B2 (en) * | 2004-04-21 | 2008-10-14 | Petroleum Habitats, L.L.C. | Assays for zero-valent transition metals in sedimentary rocks using carbon monoxide with application to oil and gas exploration |
US20090014179A1 (en) * | 2006-01-06 | 2009-01-15 | Mango Frank D | In Situ Conversion Of Heavy Hydrocarbons To Catalytic Gas |
US7608170B1 (en) * | 2005-06-10 | 2009-10-27 | Ousey John R | Method and apparatus to obtain high pressures for a continuous-flow pyrolysis reactor |
-
2007
- 2007-01-08 CN CNA2007800071486A patent/CN101395742A/en active Pending
- 2007-01-08 WO PCT/US2007/060215 patent/WO2007082179A2/en active Application Filing
- 2007-01-08 AU AU2007204728A patent/AU2007204728A1/en not_active Abandoned
- 2007-01-08 RU RU2008130831/03A patent/RU2008130831A/en unknown
- 2007-01-08 BR BRPI0706846-8A patent/BRPI0706846A2/en not_active Application Discontinuation
- 2007-01-08 US US12/159,962 patent/US7845414B2/en not_active Expired - Fee Related
- 2007-01-08 CA CA002636190A patent/CA2636190A1/en not_active Abandoned
-
2010
- 2010-12-07 US US12/962,302 patent/US8273937B2/en active Active
Patent Citations (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2387513A (en) * | 1941-08-08 | 1945-10-23 | Standard Oil Dev Co | Well logging |
US2551449A (en) * | 1949-06-15 | 1951-05-01 | Nuclear Dev Associates Inc | Method for locating deposits |
US2705417A (en) * | 1951-12-21 | 1955-04-05 | Petroleum Engineering Associat | Mineralogical analysis |
US2768793A (en) * | 1954-03-22 | 1956-10-30 | Exxon Research Engineering Co | Disintegrator for rock and the like |
US2854396A (en) * | 1954-11-24 | 1958-09-30 | Jersey Prod Res Co | Petroleum prospecting |
US3033287A (en) * | 1959-08-04 | 1962-05-08 | Pure Oil Co | Geochemical process |
US3180902A (en) * | 1961-08-10 | 1965-04-27 | Engelhard Ind Inc | Process for the hydrogenolysis of light hydrocarbons |
US3343917A (en) * | 1963-11-22 | 1967-09-26 | Pan American Petroleum Corp | Obtaining paleoenvironmental information |
US3322195A (en) * | 1964-01-20 | 1967-05-30 | Exxon Research Engineering Co | Process and apparatus for recovery of additional fuels from oil and gas wells |
US3428431A (en) * | 1965-05-12 | 1969-02-18 | Sinclair Research Inc | Geochemical petroleum exploration method |
US3719453A (en) * | 1970-11-25 | 1973-03-06 | Phillips Petroleum Co | Detection of reducing conditions in a formation as in oil prospecting |
US3752984A (en) * | 1971-12-02 | 1973-08-14 | Texaco Inc | Methods and system for detecting subsurface minerals |
US3934455A (en) * | 1974-02-13 | 1976-01-27 | The Dow Chemical Company | Apparatus for testing a sand sample |
US4108552A (en) * | 1976-06-29 | 1978-08-22 | Union Carbide Corporation | Method and system for detecting ultra-trace quantities of metal carbonyls |
US4081675A (en) * | 1976-11-08 | 1978-03-28 | Phillips Petroleum Company | Geophysical and geochemical exploration |
US4205956A (en) * | 1979-05-21 | 1980-06-03 | The International Nickel Company, Inc. | Nickel carbonyl analyzer |
US4352673A (en) * | 1979-12-28 | 1982-10-05 | Institut Francais Du Petrole | Method and device for determining the organic carbon content of a sample |
US4345912A (en) * | 1980-09-12 | 1982-08-24 | Phillips Petroleum Company | Uranium prospecting based on selenium and molybdenum |
US4334882A (en) * | 1981-04-01 | 1982-06-15 | Mobil Oil Corporation | Determination of pyrite and siderite content of formation deposits |
US4385983A (en) * | 1981-08-10 | 1983-05-31 | Chevron Research Company | Process for retorting oil shale mixtures with added carbonaceous material |
US4587847A (en) * | 1981-10-07 | 1986-05-13 | Boliden Aktiebolag | Method for indicating concealed deposits |
US4438816A (en) * | 1982-05-13 | 1984-03-27 | Uop Inc. | Process for recovery of hydrocarbons from oil shale |
US4426452A (en) * | 1982-05-27 | 1984-01-17 | Syngas Company | Volatile metal carbonyl analysis |
US4681854A (en) * | 1982-05-28 | 1987-07-21 | Phillips Petroleum Company | Geochemical oil prospecting method using in situ simulation of diagenetic processes |
US4792526A (en) * | 1982-12-21 | 1988-12-20 | Union Oil Company Of California | Method for collecting and analyzing hydrocarbons |
US4507195A (en) * | 1983-05-16 | 1985-03-26 | Chevron Research Company | Coking contaminated oil shale or tar sand oil on retorted solid fines |
US4610776A (en) * | 1984-06-29 | 1986-09-09 | Uop Inc. | Coal liquefaction process |
US4701270A (en) * | 1985-02-28 | 1987-10-20 | Canadian Fracmaster Limited | Novel compositions suitable for treating deep wells |
US4798805A (en) * | 1985-04-05 | 1989-01-17 | Geoservices, Societe Anonyme | Apparatus and process for pyrolysis and analysis of samples containing organic matter |
US5178837A (en) * | 1985-07-25 | 1993-01-12 | The British Petroleum Company P.L.C. | Rock analyzer |
US5174966A (en) * | 1989-08-14 | 1992-12-29 | Institut Francis Du Petrole | Laboratory device and method for treating rock samples |
US5082787A (en) * | 1989-12-22 | 1992-01-21 | Texaco Inc. | Method of performing hydrous pyrolysis for studying the kinetic parameters of hydrocarbons generated from source material |
US5097123A (en) * | 1990-02-07 | 1992-03-17 | Schlumberger Technology Corporation | Broad energy spectra neutron source for logging and method |
US5389550A (en) * | 1992-03-13 | 1995-02-14 | Japan National Oil Corporation | Organic substance analyzing method and apparatus using portable construction |
US5769165A (en) * | 1996-01-31 | 1998-06-23 | Vastar Resources Inc. | Method for increasing methane recovery from a subterranean coal formation by injection of tail gas from a hydrocarbon synthesis process |
US6229060B1 (en) * | 1996-07-12 | 2001-05-08 | Centre National De La Recherche Scientifique (C.N.R.S.) | Method of metathesis of alkanes and catalyst |
US20020002318A1 (en) * | 1999-06-11 | 2002-01-03 | O'rear Dennis J. | Process for conversion of well gas by disproporationation to saleable products |
US6225359B1 (en) * | 1999-12-21 | 2001-05-01 | Chevron U.S.A. Inc. | Process for conversion of natural gas and associated light hydrocarbons to salable products |
US6739394B2 (en) * | 2000-04-24 | 2004-05-25 | Shell Oil Company | Production of synthesis gas from a hydrocarbon containing formation |
US20020058581A1 (en) * | 2000-09-28 | 2002-05-16 | Fairmount Minerals, Ltd | Proppant composition for gas and oil well l fracturing |
US6666067B2 (en) * | 2001-06-07 | 2003-12-23 | Kathy Karol Stolper | Visual gas show identification method |
US20040166582A1 (en) * | 2001-07-26 | 2004-08-26 | Alain Prinzhofer | Method for quantitative monitoring of a gas injected in a reservoir in particular in a natural environment |
US20040016676A1 (en) * | 2002-07-24 | 2004-01-29 | Newton Jeffrey P. | Production of lower molecular weight dydrocarbons |
US20050082058A1 (en) * | 2003-09-23 | 2005-04-21 | Bustin Robert M. | Method for enhancing methane production from coal seams |
US7435597B2 (en) * | 2004-04-21 | 2008-10-14 | Petroleum Habitats, L.L.C. | Assays for zero-valent transition metals in sedimentary rocks using carbon monoxide with application to oil and gas exploration |
US20050250209A1 (en) * | 2004-04-21 | 2005-11-10 | Petroleum Habitats, Llc | Determining metal content of source rock during well logging |
US20060065400A1 (en) * | 2004-09-30 | 2006-03-30 | Smith David R | Method and apparatus for stimulating a subterranean formation using liquefied natural gas |
US20060121615A1 (en) * | 2004-12-07 | 2006-06-08 | Petroleum Habitats, L.L.C. | Rock assay for predicting oil or gas in target reservoirs |
US20060117841A1 (en) * | 2004-12-07 | 2006-06-08 | Petroleum Habitats, L.L.C. | Novel well logging method for the determination of catalytic activity |
US7153688B2 (en) * | 2004-12-07 | 2006-12-26 | Petroleum Habitats, L.L.C | Rock assay for predicting oil or gas in target reservoirs |
US20060191686A1 (en) * | 2005-02-25 | 2006-08-31 | Halliburton Energy Services, Inc. | Methods and compositions for the in-situ thermal stimulation of hydrocarbons using peroxide-generating compounds |
US7608170B1 (en) * | 2005-06-10 | 2009-10-27 | Ousey John R | Method and apparatus to obtain high pressures for a continuous-flow pyrolysis reactor |
US20080115935A1 (en) * | 2006-01-06 | 2008-05-22 | Mango Frank D | In situ conversion of heavy hydrocarbons to catalytic gas |
US20090014179A1 (en) * | 2006-01-06 | 2009-01-15 | Mango Frank D | In Situ Conversion Of Heavy Hydrocarbons To Catalytic Gas |
US20100200234A1 (en) * | 2006-01-06 | 2010-08-12 | Mango Frank D | In Situ Conversion of Heavy Hydrocarbons to Catalytic Gas |
US7845414B2 (en) * | 2006-01-06 | 2010-12-07 | Petroleum Habitats, L.L.C. | In situ conversion of heavy hydrocarbons to catalytic gas |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8273937B2 (en) | 2006-01-06 | 2012-09-25 | Petroleum Habitats, Llc | Generating natural gas from heavy hydrocarbons |
US8727006B2 (en) | 2010-05-04 | 2014-05-20 | Petroleum Habitats, Llc | Detecting and remedying hydrogen starvation of catalytic hydrocarbon generation reactions in earthen formations |
Also Published As
Publication number | Publication date |
---|---|
CN101395742A (en) | 2009-03-25 |
AU2007204728A1 (en) | 2007-07-19 |
US20090014179A1 (en) | 2009-01-15 |
US8273937B2 (en) | 2012-09-25 |
RU2008130831A (en) | 2010-02-20 |
WO2007082179A3 (en) | 2007-11-29 |
US7845414B2 (en) | 2010-12-07 |
CA2636190A1 (en) | 2007-07-19 |
WO2007082179A2 (en) | 2007-07-19 |
BRPI0706846A2 (en) | 2011-04-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8091643B2 (en) | In situ conversion of heavy hydrocarbons to catalytic gas | |
US8273937B2 (en) | Generating natural gas from heavy hydrocarbons | |
Shah et al. | A review of novel techniques for heavy oil and bitumen extraction and upgrading | |
US9133398B2 (en) | In-situ kerogen conversion and recycling | |
EP1276964B1 (en) | A method for treating a hydrocarbon containing formation | |
US9181467B2 (en) | Preparation and use of nano-catalysts for in-situ reaction with kerogen | |
Speight | Shale oil and gas production processes | |
NZ522211A (en) | A method for treating a hydrocarbon containing formation | |
US20080269045A1 (en) | Production of lower molecular weight hydrocarbons | |
Barenbaum et al. | Theoretical model Anderson-Schulz-Flory within the framework of studying the mechanism of polycondensation synthesis | |
Zakieva et al. | REACTIVITY OF METASTABLE WATER IN HYDROTHERMAL HEAVY CRUDE OIL AND CARBONACEOUS COMPOUNDS CONVERSIONS. | |
Al-Rubaye et al. | Environmentally Friendly Method for Enhanced Heavy Oil Recovery by In-Situ Upgrading Process Based on Catalytic Steam Injection | |
Djimasbe et al. | Development and Assisted Injection of Sub-And Supercritical Water by the Oil-Soluble Catalysts for the Intensification of Upgrading Process of the Bazhenov Oil Shale and Production of Synthetic Oil | |
Shah | Experimental optimization of the CAPRI process | |
RU2801030C2 (en) | Method for developing deposits of hard-to-recover hydrocarbons | |
WO2011140287A1 (en) | Detecting and remedying hydrogen starvation of catalytic hydrocarbon generation reactions in earthen formations | |
Djimasbe et al. | SPE-215485-MS | |
Eshiet | Production from Unconventional Petroleum Reservoirs: Précis of Stimulation Techniques and Fluid Systems | |
Nasyrova et al. | Sub-and supercritical water in the processes of conversion of Domanik rock organic matter | |
US20110275875A1 (en) | Methods and Apparatus for Promoting Production of Catalytic Generated Hydrocarbons | |
CN116409748A (en) | Hydrogen production composition, preparation method thereof and hydrogen production method | |
CN117985651A (en) | Underground hydrogen source based on hydrocarbon low-temperature catalytic hydrogen transfer and preparation method and application method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: PETROLEUM HABITATS, LLC, TEXAS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MANGO, FRANK D.;REEL/FRAME:026610/0979 Effective date: 20110712 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FEPP | Fee payment procedure |
Free format text: 7.5 YR SURCHARGE - LATE PMT W/IN 6 MO, SMALL ENTITY (ORIGINAL EVENT CODE: M2555); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |
|
MAFP | Maintenance fee payment |
Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2552); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY Year of fee payment: 8 |
|
FEPP | Fee payment procedure |
Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY |